An analysis of the possible causes of apparent compensation effects when investigating a substance under varying experimental conditions

The major causes leading to the apparent compensation effect (lgA=aE+b) at the thermal decomposition of one and the same substance in a series of experimental conditions (varying of the mass of the sample, of the heating rate, of disperseness, and at different distances from the equilibrium) were discussed. It was found that the appearance of a compensation effect at the study of the thermal decomposition of one and the same substance demonstrates the incorrect setup of the experiment, resulting in erroneous values calculated for the kinetic parameters.

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Zusammenfassung Die Hauptursachen, welche zum scheinbaren Kompensationseffekt (lgA=aE+b) der thermischen Zersetzung ein und derselben Substanz führen, wurden unter verschiedenen Versuchsbedingungen untersucht: unter Änderung der Probenmasse, der Aufheizgeschwindigkeit, der Dispersität und der Entfernung vom Gleichgewicht. Es wurde festgestellt, daß das Auftreten eines Kompensationseffekts bei der Untersuchung der thermischen Zersetzung ein und derselben Substanz auf die unrichtige Durchführung des Experiments hinweist, die zur Berechnung falscher Werte der kinetischen Parameter führt.

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Résumé On a étudié les causes principales de l'effet de compensation apparent (lgA=aE+ +b) lors de la décomposition thermique de la même substance dans différentes conditions expérimentales, en faisant varier notamment la masse du prélèvement, la vitesse du chauffage, la dispersion et l'écart à l'équilibre. On a trouvé que l'apparition d'un effet de compensation lors de l'étude de la décomposition thermique de la même substance résultait de l'exécution incorrecte de l'expérience qui mène à des valeurs fausses lors du calcul des paramètres cinétiques.

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, (lg A=aE+b) : , , , . , , .

     

Investigation of low-temperature regeneration of activated carbon

Granular activated carbon loaded with aniline,o-nitroaniline oro-nitrophenol, regenerated at relatively low temperature (450° in N₂ atmosphere), shows losses of cyclic adsorption performances (about 5 % per cycle) comparable to those occurring with standard thermal regeneration (950° in controlled atmosphere). Adsorbate build-ups and related surface modifications have been determined.

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Zusammenfassung Mit Anilin,o-Nitroanilin undo-Nitrophenol beladene, bei relativ niedriger Temperatur (450° in N₂-Atmosphäre) regenerierte granulierte Aktivkohle, zeigt zyklische Verluste der Adsorptionsleistung (etwa 5 % je Zyklus), welche mit den bei thermischer Standard-Regenerierung (950° in gesteuerter Atmosphäre) vorkommenden vergleichbar sind. Der Aufbau der Adsorbate und die damit verbundenen Oberflächenänderungen wurden bestimmt.

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Résumé Le charbon actif en granulés, chargé d'aniline, d'o-nitroaniline et d'o-nitrophénol, régénéré à une température relativement faible (450° dans une atmosphère d'azote) montre des pertes de rendement d'adsorption cyclique (environ 5 p.c. par cycle) comparables à celles qui ont lieu lors de la régénération thermique standard (950° en atmosphère contrôlée). On a déterminé la constitution des adsorbats et les modifications relatives de surface.

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, , -, - – 450° . , ( 5% ) – 950° . .

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Work supported by IRSA-CNR, contract no. 77.01823.11.

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Thanks are due to Mr. L. Pace for skilful contribution to the experimental work.     

Stabilization of reaction products of ureas with polyfluoro ketones

Conclusions Polyfluorinated tetrahydro-1,3,5-oxadiazine derivatives were obtained by the condensation of urea and thiourea with polyfluoro ketones.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2168–2169, September, 1977.     

Einführung von Carboxylgruppen in vernetztes Polystyrol

Ohne Zusammenfassung     

Photochemical and thermal transformations of azomethine imines

The thermal and photochemical fragmentations of a few bisazoalkenes have been investigated. 2-Phenyl-4,5-disubstituted-1, 2,3-triazoles were obtained both in the thermolysis and photolysis of 1, 2-bisphenylazo-(4, 4′-dichloro) stilbene, 1, 2-bisphenylazo(4, 4′-dimethoxy)stilbene, 1, 2-bisphenylazocyclohexene and o-(phenylazo) phenyldiazocyanide. Both 2, 3-bisphenylazo-2-butene and 1, 2-bisphenylazoethylene failed to undergo either photolysis or thermolysis in the expected manner. However, 2, 3-bisphenylazo-2-butene underwent an acid-catalysed valence isomerisation to anhydro 1-phenylimino-2-phenyl-4, 5-dimethyl-1, 2, 3-trizolium hydroxide, which on photolysis gave 2-phenyl-4, 5-dimethyl-1, 2, 3-triazole. The same iminotriazolium intermediate gave a cycloadduct, 2, 6-diphenyl-3, 3a-dimethyl-4, 5-dicarbomethoxypyrazolino [2.3.c][1.2.3] triazole, on treatment with dimethyl acetylenedicarboxylate, whereas treatment with carbon disulphide gave 2-phenyl-4, 5-dimethyl-1, 2, 3-triazole. Both photolysis and thermolysis of C-biphenylene-N^α(4-chlorophenyl)-N^β-cyanoazomethine imine gave 9-fluorenone-N- (4-chlorophenyl) anil. Photolysis of 1, 2-bisphenylazoacenaphthylene in methanol gave acenaphthenequinone monophenylhydrazone.     

Dissociative ionization of methyl-substituted hydroxyquinolines

The mass spectra of the following methyl-substituted hydroxyquinolines have been studied in the range of energies of the ionizing electrons of 15–50 eV: 2-hydroxy-4-methylquinoline, 6-hydroxy-2-methylquinoline, 6-hydroxy-4-methylquinoline, 8-hydroxy-2-methylquinoline, 8-hydroxy-4-methylquinoline, 2,6-dihydroxy-4-methylquinoline, and 4,6-dihydroxy-2-methylquinoline. It has been shown that the processes of dissociative ionization for the series of compounds investigated take place exclusively from the keto forms of the molecular ions. The stability to electron impact is determined largely by the degree of enolization of the structures considered. The values of the selective decomposition are given and a scheme is proposed for the identification of the isomeric methyl-substituted hydroxyquinolines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 972–978, July, 1973.     

Simple method for the preparation of 1-oxo-1-chlorophospholenes

Conclusions A new and simple method has been found for the synthesis of 1-oxo-1-chlorophospholenes by the reaction of phosphorus trichloride, a diene, and an oxygen-donor compound, the best of which is acetone.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1847–1848, August, 1972.